1;Science of Synthesis: Knowledge Updates 2016/2;1 2;Title Page;6 3;Copyright;8 4;Preface;9 5;Abstracts;11 6;Science of Synthesis Knowledge Updates 2016/2;19 7;Table of Contents;21 8;1.2.7 Radical-Based Palladium-Catalyzed Bond Constructions;35 8.1;1.2.7.1 Method 1: Reactions Involving Palladium(I) Species;35 8.1.1;1.2.7.1.1 Variation 1: Synthesis of Organometallic Palladium(I) Complexes;35 8.1.2;1.2.7.1.2 Variation 2: Reactions Involving Palladium(I) Precatalysts;42 8.1.3;1.2.7.1.3 Variation 3: Cross-Coupling Reactions;50 8.1.4;1.2.7.1.4 Variation 4: Carbonylation Reactions;61 8.1.5;1.2.7.1.5 Variation 5: Cyclization Reactions;76 8.1.6;1.2.7.1.6 Variation 6: Atom-Transfer Reactions;82 8.2;1.2.7.2 Method 2: Reactions Involving Palladium(III) Species;96 8.2.1;1.2.7.2.1 Variation 1: Synthesis of Organometallic Palladium(III) Complexes;96 8.2.2;1.2.7.2.2 Variation 2: C-H Activation Reactions Involving Palladium(III);106 8.2.3;1.2.7.2.3 Variation 3: C-F Bond-Constructing Reactions Involving Palladium(III);113 8.2.4;1.2.7.2.4 Variation 4: Reactions Involving Phenyl or Benzoyl Radicals;116 8.2.5;1.2.7.2.5 Variation 5: Asymmetric Aza-Claisen Rearrangements;126 8.3;1.2.7.3 Method 3: Reactions Involving Palladium(I) and Palladium(III) Species;129 8.4;1.2.7.4 Method 4: Miscellaneous Reactions;132 9;2.11.15 C(sp3)-H Functionalization by Allylic C-H Activation of Zirconocene Complexes;147 9.1;2.11.15.1 Method 1: Synthesis of Conjugated Dienes from Nonconjugated Dienes;152 9.1.1;2.11.15.1.1 Variation 1: From Nonheteroatom-Substituted Alkenes;152 9.1.2;2.11.15.1.2 Variation 2: From Nonconjugated Dienes Bearing an Alkoxy Substituent;153 9.2;2.11.15.2 Method 2: Synthesis of Trienes;156 9.3;2.11.15.3 Method 3: Synthesis of Homoallylic Alcohols;157 9.3.1;2.11.15.3.1 Variation 1: From Acid Chlorides without Ligand Exchange;157 9.3.2;2.11.15.3.2 Variation 2: From Acid Chlorides with Ligand Exchange;158 9.3.3;2.11.15.3.3 Variation 3: From Aldehydes without Ligand Exchange;160 9.3.4;2.11.15.3.4 Variation 4: From Aldehydes with Ligand Exchange;162 9.4;2.11.15.4 Method 4: Diastereoselective Synthesis of Homoallylic Amines;163 9.5;2.11.15.5 Method 5: Diastereoselective Synthesis of 1,4-Homoallylic Diols;164 9.5.1;2.11.15.5.1 Variation 1: From Grignard Reagents;164 9.5.2;2.11.15.5.2 Variation 2: From Terminal Alkenes;166 9.6;2.11.15.6 Method 6: Synthesis of 1,2-Disubstituted Cyclopropanols;167 9.7;2.11.15.7 Method 7: Synthesis of Substituted Allylic Derivatives from Unsaturated Fatty Alcohols;167 9.8;2.11.15.8 Method 8: Selective Reduction of the Double Bond of ?-Ene Dihydrofurans and Dihydropyrans;169 9.9;2.11.15.9 Method 9: Synthesis of Acyclic Fragments Possessing an All-Carbon Quaternary Stereogenic Center;170 9.9.1;2.11.15.9.1 Variation 1: From ?-Ene Cyclopropanes;170 9.9.2;2.11.15.9.2 Variation 2: From Alkylidenecyclopropanes;173 9.9.3;2.11.15.9.3 Variation 3: From ?-Alkenylcyclopropanes Bearing a Leaving Group;176 10;2.11.16 Synthesis and Reactivity of Heteroatom-Substituted Vinylzirconocene Derivatives and Hetarylzirconocenes;181 10.1;2.11.16.1 General Preparation of Vinylzirconocene Derivatives;182 10.2;2.11.16.2 General Reactivity of Vinylzirconocene Derivatives;184 10.3;2.11.16.3 Preparation of Vinylzirconocene Derivatives from Heteroatom-Substituted Alkenes;185 10.3.1;2.11.16.3.1 Method 1: From Alkenyl Halides;186 10.3.2;2.11.16.3.2 Method 2: From Aryl Halides;188 10.3.3;2.11.16.3.3 Method 3: From Enol Sulfonates;192 10.3.4;2.11.16.3.4 Method 4: From Enol Ethers and Silyl Enol Ethers;194 10.3.5;2.11.16.3.5 Method 5: From Sulfides, Sulfoxides, and Sulfones;196 10.3.6;2.11.16.3.6 Method 6: From Carbamates;200 10.3.7;2.11.16.3.7 Method 7: From Dienyl Systems;202 11;2.12.17 The Role of Solvents and Additives in Reactions of Samarium(II) Iodide and Related Reductants;211 11.1;2.12.17.1 Synthesis of Samarium(II) Reductants;211 11.1.1;2.12.17.1.1 Samarium(II) Iodide;212 11.1.1.1;2.12.17.1.1.1 Method 1: Synthesis in Tetrahydrofuran from Samarium an